Composition of enhanced affinity for dyes



.bilities of various cellulose which are veryunfavorable, we propose to solve the problem basic dyes which tate'itsell! slowly Patented Aug. 13, 1935 ooMPosI'rm QFgmaanoeaarrrmry es R. Foidyce, "Rochester, N. Y., assignors to Eastman Kodakflompanyg- Garl J. Malm and Char] Rochester,

I 'Ihe'present invention relates toa composition of matter comprising a fatty acid ester of celluployed'commerclally for filaments and skins or sheets." v

- {At'the present time large quantities of the secon whlchthey were employed. 'In :many cases the cellulose acetate would only be dyed to a comparatively light-shade upontreatment with the dye. I 'It has 'been stated that the: fastness' "of the basic colors on cellulose acetate silk appears to follow closely the efifinity otathe dyestufl. for the Silk. Thus not only the cellulose acetate only capable of being dyed but the color would probitedperiodOf time. l A In view of this variation in the dye susceptiacetates,;many of of non-uniformity of. dyeing presented by the above facts by preparing a composion having a satisfactory aifinity to already existing. dyes, in contrast to attempting tosolvethis "might e equally. effective with Ian kinds of celluloseacetate materials. which maybe employed in this connection. One'object of our invention; is to prepare a composition containing. cellulose acetate which may be readily andseasily dyed by will only' dye the cellulose aceif at all.

Wefha've found that a composltion compri'sing "cellulose acetate containing approximately 10% to approximately bajSEd onthe weight of the cellulose acetate) of a "celluloseiacetaterdican.

'boxylate' such as cellulose acetate phthalate is readily dyed by basic dyes and that a deep coloraltionmay be obtained if desired'in a comparative} N. Y'.,ia corporationof Newfllorkf- No Drawing. Application December 17,1932;

Serial No.'647;828 8'Claims. (0!..106-40) l-dfsll'k'e {also for two; minutes.' The products contai jn'o, cellulose acetate phthalateaexhi 'I'he .cellulo free at a a ol t pn. a p dye. bath consisting of r .05, f ram of an 'fanthraquincgnedyeflof the disperspl type such as'SgjR. A.

ly short period. We have found." the time necessaryto obtain a given shade withthis confliposition' containing a jdicarboxy'lic 'acid e'ste'r'fof cellulose is considerably'lesswith a g'ivenfdye bath than has been formerly re'quiredjto procure, that shadewhen cellulose"acetatewasemployed. 1

The following examples are illustrative of the susceptibility t cye's ofj he ,compos fi o ii 6m? bodied in the present inventi n: y

' EwdiflpZe 1.;% s'olutions of a cellulose acetate' phthalate "containing". 31% 'phthalyl andfia cellulose acetate oi 38.% actylcjontentlinac one were separately ipreparedgj 'Ifhese solutions ere mixed in the.proportionf of 'one part of",.the.ace

jtate.phthalatesolution'to five. p rts. of the'agotate solution and filaments were spu'n'and skins were coated iiromythislmikture. v l ucts were! also prepared from the Icelluloseaacel- .t'ateand cellulose acetate p. th'alatq wertreated' .in a warm basic fuchsin solution ,forftw'o minutes and. a deep red coloration o'fthe products resulted.

Corresponding] pr d.'-

The,- products 'prep'a'red using I eeuuigs ace a e galone were treated'with a basic ,f. uchsin solution composition and temperature, as before,

ly noticeable red coloration. 5 1 se acetate phthalate employed was ,base, such method and the products-resulting prepared byjftreatinga cellulose acetatef'having v .iree and 'available'hydroxylgroups with phthalic anhydride inthe presence. of a tertiaryaorganic therefroni being disclosed nd olaimedinYMalm Exampl lose acetate was prepared and divided. intoltw o portions. To one pol tion10%;of-a cellulose aceltate-phthalate .;(based*qn the Weight of the cel ;-lulose acetate) was addedtheretor The two solutions. were. :then formed into filaments-q by projectingieaohthrough aspinneret into an evaporative atmosphere in the well known -manner.. :"The twoi-filamentswwere then treated in .ascouring of neutral soap and 3 grams of ammonia-sold tion (approximately 28%) for every 100 grams of yarnor filament" to be. treated. The mass was maintained at-a temperature of'80-85" C. with gentle agitation forxabout minutes. The filaments were removed from the bath and rinsed It wa hen lace in a and Waringapplication Serial Na;- 330, 2 5 2 filed +A 20% solutionor dope in acetone an dir a mmer l cetoner c b lu- I gbath,whichicontained'3jlitersoi water, 6 grams a greaterafllnity than does cellulose acetate: basic dyestuffssuch veloped colors such formula:

2 I 7 blue IV powder, which dye may be represented by the formula NHCH:

-o H 0 l NHCH:

45 grams of soda ash, a liter of softwater'. The bath was at ordinary temperaturewhen the yarn-=was placed'therein. It was then brought up to atemperature of C. over a period of '20 minutes and maintained at that temperature'for taken place on the yarn comprising only the cellulose acetate. When samples of the two yarns were dyed separately it was, foundthat the yarn containing the cellulose acetate phthal'a'te dyed to a given shade inmuch less time than the yarn from which it had been omitted. i

, Instead of the acetate-phthalates ofcellulose other cellulose esters of dicarboxylic acids may be employed in the present invention. "Forins'ta'nc'e a cellulose acetate succinate such'asgdescribed and claimed in Malmjand Waring applications serial Nos; 380,252 and 627,150 or a cellulose acetate dicarboxylate in which a heterogeneously linked dicarboxylic acid' is employed suchj'as 'a cellulose acetate diglycollate as described and claimed in Malm and Fordyce application Serial 'No. 627,147 may be employed. These cellulose acetate 'dicarboxylates are commonly prepared by reacting upon a cellulose acetate containing free and available hydroxyl groups with adicarboxylic acid anhydride and an amount of a tertiary organic base such' as' pyridine, quinoline or the like sufllcient to esterify the second carboigrl group, and then treating the resulting product which is a cellulose acetatepyridine dicarboxylate with an acid such as acetic which is strong enoughto remove the pyridine from the com- 'In addition to testing the composition forming the subject of the a present invention by colorin it by dispersol methods of dyeing, it was also compared with ordinary acetate by vat dyeing.

filament of cellulose acetate conwas dyed in the same bath as a cellulose acetate, the vat dye employed being ciba phthalate was found to exhibit ash'ade considerably darker thantheillament containing cellulose acetate as the only cellulose ester present. The present compositionhas been found to have for the following types of dyes as brilliant cresyl blue BB, color index No. 1877,

phthalic anhydride dyestuffs such as rhodamine B base, color index No. 749, diazotized and: de-

as SRA black IV having the Filaments prepared from our composition may be employed for the manufacture of fabrics either entirely or together with threads of other maposition will exhibit a resist 6 cc. of Turkey red oil and;

. navy blue BN. The filament containing the cellulose acetate a fatty" acid terial to give various eifects. For instance, if a fabric is made containing both yarns or filaments of the present composition and of cellulose acetate, color effects will be procured upon the dyeing of that material. Fabrics may also be prepared from threads of -the present composition totgether w'ithithreads of .rayonjor cottomor both, in which fabrics the threads of the present comeffect when the fabric is treated for instance with a direct cotton Our composition may also be employed for the v preparation of sheeting which may, if desired, 'be

' dyed and employed in any capacity desired, such 1 as wrapping "material, etc.

15 minutes with gentle agitation. It was found that the yarn containing the cellulose acetate-phthalate had almost ex-" hausted the dye bath before much dyeing'lhad- As is illustrated by the examples, our preferred "composition comprises cellulose acetate containvarious purposesffor which cellulose ester compositions 'aref employed such as artiiicial leather, photographic film 'support,- lacquers, plastic s,adhesives etc. it beingespecially adapted-for use in instances wh re coloring; of the estercomposition is desired. They maybe mixed with various ma- .terials such as plasticizers other cellulosederivatives whether thefacetate, nitrate, acetatepropionate v or an etherof cellulose, resins, waxes, gums, fillers, -etc., theonly limitation being that the material must be, compatible with the present composition,

- If desired one may'employ some other fatty f acid esterof cellulose than eellulo se .-acetate in the composition-accordingto thisinvention -.;Esjterssuchqas cellulose acetate propionate; cellulose acetate-butyrate, cellulose propionate and cellulose butyrate suggest themselves to the .in-

dividual as being-suitablein the present composition to "replace-all ora-partof thezcellulose acetate which isiusually employed.-2 Y

Various other-modifications, which are e l ar- .ent to those skilled in the art, are also within the scope of the present invention... 1 wr The term"colloidized as applied-to products or materials herein refers to a material which has been dlssolvedyinra' which solutionthe' solvent has bemevaporated. For example if the composition constituting the present'in'vention we're dissolved in acetone and a filament weref'f ormed "irornf this solution 'by evaporative spinning the material formed would be' regarded ascolloidized' j We claim-as' our inventions: v rjjz, 1. -A composition of matter which comprisesia i mi'?aid este r l l and a n qsesgesie a containing adicarboxylic"acid'radical, one of, the

fcarboxyl'groupsv of which is. unesterifiedfthe latter being present in aproportion ,sumcient to give substantially greater sus'cepti 2.A compo'sition.-Of matter which comprises the carboxyl groups of which is .unesteriiled, 5 the "th f does cellulose'acetate.

3. A. composition" of matter whichlcomprises "a fatty acid ester 1 0i cellulose ,and cellulose acetate-phthalate having an unesteriiled carboxyl volatile solvent and from v .fi w l e I I with basicfdyesfthan does celluloseacetate. ff

ester of cellulose" a cellulose ester containing a. phthalic acii fadical, one' of group, the latter being present in a. proportion sufficient to give substantially greater susceptibility to dyeing with basic dyes, than'does cellulose acetate. f v

4. An artificial silk filament which comprises a fatty acid ester of cellulose and a cellulose ester containing a dicarboxylic acid radical, one of the carboxyl groups of which is unesterified, the latter being present in a proportion sufiicient to give substantially greater susceptibility to dyeing with basic dyes, than does cellulose acetate.

5. A colloidized article of manufacture which comprises a fatty acid ester of cellulose and a cellulose ester containing a phthalic acid radical, one of the carboxyl groups of which is unesterified, the latter being present in a proportion sufficient to give substantially greater susceptibility to dyeing with basic dyes, than does cellulose acetate.

6. A dyed composition of matter which comprises a fatty acid ester of cellulose and a cellulose ester containing a dicarboxylic acid radical, one of the carboxyl groups of which is unesterified the latter being present in a proportion sufficient to give substantially greater susceptibility to dyeing with basic. dyes, than does cellulose acetate.

7. A dyed artificial silk filament which comprises a fatty acid ester of cellulose and a cellulose ester containing a phthalic acid radical, one

of the carboxyl groups of which is unesterified, the latter being present in a proportion sufiicient to give substantially greater susceptibility to dyeing with basicdyes, than does cellulose acetate.

CARL J. MALM. CHARLES R. FORDYCE.

dyeing with basic dyes, 

